Issue 7, 2022

Rh2(ii)-catalyzed enantioselective intramolecular Büchner reaction and aromatic substitution of donor–donor carbenes

Abstract

The chiral dirhodium(II) tetracarboxylate-catalyzed enantioselective intramolecular Büchner reaction of donor/donor-carbenes was reported and a series of valuable chiral polycyclic products were synthesized. Both aryloxy enynones and diazo compounds were efficient carbene precursors for this reaction. Excellent yields (up to 99%) and outstanding enantioselectivities (up to >99% ee) were achieved under standard conditions. For furyl substituted chiral cyclohepta[b]benzofurans bearing a substituent at the C4 position on cycloheptatrienes, control reactions showed that the chiral Büchner products could slowly racemize either under dark or natural light conditions. A diradical-involved mechanism rather than a zwitterionic intermediate was proposed to explain the racemization. Furthermore, furyl substituted chiral fluorene derivatives were obtained via asymmetric aromatic substitution when biaryl enynones were employed as carbene precursors.

Graphical abstract: Rh2(ii)-catalyzed enantioselective intramolecular Büchner reaction and aromatic substitution of donor–donor carbenes

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Sep 2021
Accepted
19 Jan 2022
First published
19 Jan 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 1992-2000

Rh2(II)-catalyzed enantioselective intramolecular Büchner reaction and aromatic substitution of donor–donor carbenes

D. Zhu, T. Cao, K. Chen and S. Zhu, Chem. Sci., 2022, 13, 1992 DOI: 10.1039/D1SC05374D

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